CN1245807A - Preparation method of silicane whose alpha-position related to silicon atom possesses tertiary alkyl radical - Google Patents
Preparation method of silicane whose alpha-position related to silicon atom possesses tertiary alkyl radical Download PDFInfo
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- CN1245807A CN1245807A CN99111538A CN99111538A CN1245807A CN 1245807 A CN1245807 A CN 1245807A CN 99111538 A CN99111538 A CN 99111538A CN 99111538 A CN99111538 A CN 99111538A CN 1245807 A CN1245807 A CN 1245807A
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- general formula
- alkyl
- chlorine
- silane
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- 238000002360 preparation method Methods 0.000 title abstract description 5
- 229910052710 silicon Inorganic materials 0.000 title abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title abstract 3
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 9
- 239000000460 chlorine Chemical group 0.000 claims abstract description 9
- 150000004795 grignard reagents Chemical class 0.000 claims abstract description 8
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 7
- 239000011737 fluorine Substances 0.000 claims abstract description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 3
- -1 phosphine alkane Chemical class 0.000 claims description 24
- 229910000077 silane Inorganic materials 0.000 claims description 21
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052723 transition metal Inorganic materials 0.000 claims description 8
- 239000007818 Grignard reagent Substances 0.000 claims description 7
- 239000013522 chelant Substances 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 150000003624 transition metals Chemical class 0.000 claims description 7
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- 239000005749 Copper compound Substances 0.000 claims description 4
- 150000001880 copper compounds Chemical class 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 239000011630 iodine Substances 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 125000001153 fluoro group Chemical group F* 0.000 abstract 2
- 150000004756 silanes Chemical class 0.000 abstract 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 abstract 1
- QYJPSWYYEKYVEJ-FDGPNNRMSA-L copper;(z)-4-oxopent-2-en-2-olate Chemical compound [Cu+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O QYJPSWYYEKYVEJ-FDGPNNRMSA-L 0.000 description 13
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 10
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 8
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 229910052749 magnesium Inorganic materials 0.000 description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 7
- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 description 7
- 238000005660 chlorination reaction Methods 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 4
- 229960003280 cupric chloride Drugs 0.000 description 4
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- DYBPJIVJNKMNHL-UHFFFAOYSA-N 1,1'-biphenyl;dichlorosilicon Chemical compound Cl[Si]Cl.C1=CC=CC=C1C1=CC=CC=C1 DYBPJIVJNKMNHL-UHFFFAOYSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- YMHOBZXQZVXHBM-UHFFFAOYSA-N 2,5-dimethoxy-4-bromophenethylamine Chemical compound COC1=CC(CCN)=C(OC)C=C1Br YMHOBZXQZVXHBM-UHFFFAOYSA-N 0.000 description 2
- PSYGHMBJXWRQFD-UHFFFAOYSA-N 2-(2-sulfanylacetyl)oxyethyl 2-sulfanylacetate Chemical compound SCC(=O)OCCOC(=O)CS PSYGHMBJXWRQFD-UHFFFAOYSA-N 0.000 description 2
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 description 2
- 239000005046 Chlorosilane Substances 0.000 description 2
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- VURFVHCLMJOLKN-UHFFFAOYSA-N Diphosphine Natural products PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 241000545067 Venus Species 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 2
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229960004643 cupric oxide Drugs 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000004508 fractional distillation Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 description 2
- MHYGQXWCZAYSLJ-UHFFFAOYSA-N tert-butyl-chloro-diphenylsilane Chemical group C=1C=CC=CC=1[Si](Cl)(C(C)(C)C)C1=CC=CC=C1 MHYGQXWCZAYSLJ-UHFFFAOYSA-N 0.000 description 2
- KNSVRQSOPKYFJN-UHFFFAOYSA-N tert-butylsilicon Chemical compound CC(C)(C)[Si] KNSVRQSOPKYFJN-UHFFFAOYSA-N 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical compound SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 2
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- HMVFITKXZCNKSS-UHFFFAOYSA-N 2-methoxy-n,n-dimethylethanamine Chemical compound COCCN(C)C HMVFITKXZCNKSS-UHFFFAOYSA-N 0.000 description 1
- VIVLBCLZNBHPGE-UHFFFAOYSA-N 3-methoxy-n,n-dimethylpropan-1-amine Chemical compound COCCCN(C)C VIVLBCLZNBHPGE-UHFFFAOYSA-N 0.000 description 1
- UWKKBEQZACDEBT-UHFFFAOYSA-N CCCC[Mg] Chemical group CCCC[Mg] UWKKBEQZACDEBT-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 101100226116 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) esa-1 gene Proteins 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- UNRQTHVKJQUDDF-UHFFFAOYSA-N acetylpyruvic acid Chemical compound CC(=O)CC(=O)C(O)=O UNRQTHVKJQUDDF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- FQEKAFQSVPLXON-UHFFFAOYSA-N butyl(trichloro)silane Chemical group CCCC[Si](Cl)(Cl)Cl FQEKAFQSVPLXON-UHFFFAOYSA-N 0.000 description 1
- BCEPTKBQFGPAIQ-UHFFFAOYSA-N butyl-chloro-diethylsilane Chemical group CCCC[Si](Cl)(CC)CC BCEPTKBQFGPAIQ-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- NJKDOKBDBHYMAH-UHFFFAOYSA-N dibutyl(dichloro)silane Chemical compound CCCC[Si](Cl)(Cl)CCCC NJKDOKBDBHYMAH-UHFFFAOYSA-N 0.000 description 1
- BYLOHCRAPOSXLY-UHFFFAOYSA-N dichloro(diethyl)silane Chemical compound CC[Si](Cl)(Cl)CC BYLOHCRAPOSXLY-UHFFFAOYSA-N 0.000 description 1
- LDCUNMZSOUMLRQ-UHFFFAOYSA-N dichloro-(cyclohexylmethyl)-methylsilane Chemical compound C[Si](Cl)(Cl)CC1CCCCC1 LDCUNMZSOUMLRQ-UHFFFAOYSA-N 0.000 description 1
- UFVFNJHZBMHRCO-UHFFFAOYSA-N dichloro-decyl-methylsilane Chemical compound CCCCCCCCCC[Si](C)(Cl)Cl UFVFNJHZBMHRCO-UHFFFAOYSA-N 0.000 description 1
- QFHGBZXWBRWAQV-UHFFFAOYSA-N dichloro-ethyl-phenylsilane Chemical compound CC[Si](Cl)(Cl)C1=CC=CC=C1 QFHGBZXWBRWAQV-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- FKKWHMOEKFXMPU-UHFFFAOYSA-M magnesium;2-methylbutane;chloride Chemical compound [Mg+2].[Cl-].CC[C-](C)C FKKWHMOEKFXMPU-UHFFFAOYSA-M 0.000 description 1
- YCCXQARVHOPWFJ-UHFFFAOYSA-M magnesium;ethane;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C YCCXQARVHOPWFJ-UHFFFAOYSA-M 0.000 description 1
- FQGYCXFLEQVDJQ-UHFFFAOYSA-N mercury dicyanide Chemical compound N#C[Hg]C#N FQGYCXFLEQVDJQ-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N mono-n-propyl amine Natural products CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- QATBRNFTOCXULG-UHFFFAOYSA-N n'-[2-(methylamino)ethyl]ethane-1,2-diamine Chemical compound CNCCNCCN QATBRNFTOCXULG-UHFFFAOYSA-N 0.000 description 1
- DIHKMUNUGQVFES-UHFFFAOYSA-N n,n,n',n'-tetraethylethane-1,2-diamine Chemical compound CCN(CC)CCN(CC)CC DIHKMUNUGQVFES-UHFFFAOYSA-N 0.000 description 1
- VGIVLIHKENZQHQ-UHFFFAOYSA-N n,n,n',n'-tetramethylmethanediamine Chemical compound CN(C)CN(C)C VGIVLIHKENZQHQ-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- LFAGQMCIGQNPJG-UHFFFAOYSA-N silver cyanide Chemical compound [Ag+].N#[C-] LFAGQMCIGQNPJG-UHFFFAOYSA-N 0.000 description 1
- 229940098221 silver cyanide Drugs 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- JSQJUDVTRRCSRU-UHFFFAOYSA-N tributyl(chloro)silane Chemical group CCCC[Si](Cl)(CCCC)CCCC JSQJUDVTRRCSRU-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
- C07F7/121—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20
- C07F7/122—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20 by reactions involving the formation of Si-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/0827—Syntheses with formation of a Si-C bond
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a process for the preparation of silanes of the general formula 1 RmRn1SiX4-m-n(1) by reaction of Grignard reagents of the general formula 2 R1MgX1(2) with silanes of the general formula 3 RmSiX4-m(3) wherein R denotes C1- to C10-hydrocarbon radicals optionally substituted by fluorine, chlorine or cyano radicals, R1, in the alpha -position relative to the silicon atom, denotes tertiary C4- to C30-hydrocarbon radicals optionally substituted by fluorine, chlorine or cyano radicals, X and X1 each denote chlorine, bromine or iodine, m denotes the values 2 or 3 and n denotes the values 1 or 2.
Description
The present invention relates in the preparation method who has the silane of tertiary hydrocarbon base with respect to the alpha-position place of Siliciumatom.
In silane compound, yes by the silane of often studying and using for the silane that the Thexyl-and the tertiary butyl replace.The silane that Thexyl-replaces mainly is by Si-H compound and 2, and the hydrosilylation reactions between 3-dimethyl-2-butylene prepares.This is described among the EP-A-177 454.But,, have some to be difficult to remove in these by products because the migration of two keys can produce unwished-for by product in these reactions.
The reaction that A.Shirata (Tetrahedron Lett.30 (1989) 6393) has described by halosilanes and tertiary butyl chlorination magnesium prepares the silane that the tertiary butyl replaces, and wherein catalyzer is necessary.
US5,332,853 have described from the initial method for preparing t-butylsilane of tert-butyl lithium.Though this method has goodish productive rate because the price of alkyl lithium compounds is very high, so its almost without any economic worth.In addition, even in very rare solution, handling fire-hazardous tert-butyl lithium on technical scale also is extremely expensive and the very difficult safety that guarantees.
For increasing the productive rate that the reaction of more cheap metal alkyl tertiary butyl magnesium Ge Liya (Grignard) reagent and halosilanes generates corresponding t-butylsilane, the catalytic activity of having tested various metal-salts.According to EP-A-405 560, obtained gratifying result with the catalyzer that comprises prussiate or thiocyanate-, as silver cyanide, mercury cyanide (II), cupric cyanide (I), Sodium Thiocyanate 99 or cupric thiocyanide (I), but these reactions mostly relate to safety, environment and handling problem.In addition, the silane that makes by prussiate and thiocyanate-has not pleasant smell usually, and this has reduced the quality or the usability of corresponding silane.
When still acceptable halogen-transition-metal catalyst is made us in use, only there is at present the Grignard compound of in EP-A-542 250, describing to react, the productive rate that can realization makes us accepting with the reaction of hydrogenous chlorosilane and Grignard compound of in EP-A-656 363, describing and the chlorosilane that comprises at least three chlorine atoms.
The objective of the invention is to overcome the defective of prior art, and by simply, the economic method for preparing silane particularly, this method is that preparation has the silane of tertiary hydrocarbon base on the alpha-position with respect to Siliciumatom as initiator to comprise the halosilanes that is less than 3 halogen atoms.
The present invention relates to prepare the method for the silane of general formula 1:
R
mR
1 nSiX
4-m-n(1) it is the Grignard reagent that makes general formula 2 when transition-metal catalyst and the non-proton chelate compound of inertia exist
R
1MgX
1(2) with the silane reaction of general formula 3,
R
mSiX
4-m(3) wherein:
The optional C that is replaced by fluorine, chlorine or cyano group of R representative
1-C
10Alkyl,
R
1On alpha-position with respect to Siliciumatom, the optional C that is replaced by fluorine, chlorine or cyano group of its representative
4-C
30The tertiary hydrocarbon base,
X and X
1Represent chlorine, bromine or iodine respectively,
M represents 2 or 3 numerical value, and
N represents 1 or 2 numerical value.
The method according to this invention, can high yield and purity obtain the silane of general formula 1.Reaction times is short.When selecting catalyst and chelate compound, can easily consider toxicology character.
The example of alkyl R is an alkyl, as methyl, ethyl, n-propyl group, sec.-propyl, n-butyl, sec-butyl and octadecyl; Thiazolinyl is as vinyl; Cycloalkyl is as cyclohexyl and methylcyclohexyl; Aryl is as phenyl; Aralkyl is as benzyl, styroyl, phenyl nonyl and 2-phenyl propyl; And alkaryl, as tolyl.
The example of the alkyl R that is substituted is and the alkyl that replaces of halogen particularly, as 3,3,3-trifluoro propyl, 3,3,4,4,5,5,6,6,6-nine fluorine hexyls and neighbour-, right-and-chloro-phenyl-.
Preferred radicals R is C
1-C
6Alkyl and phenyl.
R
1Formula-CR preferably
2 3The tertiary hydrocarbon base, R wherein
2The connotation that has R independently of each other.Radicals R
2C preferably
1-C
6Alkyl, particularly methyl and ethyl and C
1-C
6The alkylidene group phenyl.
Radicals R
1Preferred example be the tertiary butyl, 1,1-dimethyl propyl or 1,1-diethyl propyl group and 1,1-dimethyl-2-phenylethyl.
The preferred example of the silane of general formula 1 is t butyldimethylsilyl chloride, tertiary butyl diethyl silicon chlorides, tertiary butyl di-n-butyl silicon chlorides, the positive decyl methyl of tertiary butyl silicon chlorides, the tertiary butyl (cyclohexyl-methyl) methyl silicon chlorides, tert-butyl diphenyl silicon chlorides, tertiary butyl aminomethyl phenyl silicon chlorides, 1,1-dimethyl benzyl dimethyl chlorination silicon and 1,1-dimethyl propyl dimethyl chlorination silicon.
The preferred example of the Grignard reagent of general formula 2 is tertiary butyl chlorination magnesium, tertiary butyl bromination magnesium, 1,1-dimethyl propyl magnesium chloride, 1,1-diethyl propyl group magnesium chloride and 1,1-dimethyl-2-propyl group ethylmagnesium chloride.
The preferred example of the silane of general formula 3 is dimethyl silicon dichloride, diethyl silicon dichloride, di-n-butyl silicon dichloride, positive decyl methyl dichloro silicon, (cyclohexyl methyl) methyl dichloro silicon, phenylbenzene silicon dichloride or ethylphenyl silicon dichloride.
The preferred transition-metal catalyst that uses is that oxidation level is+1 copper compound, as chlorinated ketone (I), cupric bromide (I), cupric iodide (I) or cupric oxide (I); Oxidation level is+2 copper compound, as cupric chloride (II), methyl alcohol copper (II), venus crystals (II) or cupric acetylacetonate (II); And zn cpds, as zinc chloride, zinc bromide, acetopyruvic acid zinc or zinc chloride-ether complex.
The addition activation can realize by the non-proton chelate compound of inertia, and this compound is preferably selected from glycol ether, many (organic amines) or many (organic phosphine alkane) and their assorted substitutive derivative.These compounds can add separately or add with the form of mixture.
The non-proton chelating glycol ether of used inertia is preferably open chain ethylene glycol bisthioglycolate C
1-C
12Alkyl oxide, particularly ethylene glycol bisthioglycolate C
1-C
6Alkyl oxide, as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, Diethylene Glycol dibutyl ether, triethylene glycol dimethyl ether or TEG dimethyl ether, or ring-type glycol ether, particularly [12] hat-4 or [18] hat-6.
The non-proton chelating of inertia many (organic amines) is N preferably, N, N ', N '-four C
1-C
12Alkyl-C
1-C
3Alkylenediamine, as N, N, N ', N '-tetramethyl-methylene diamine, N, N, N ', N '-tetramethylethylened and N, N, N ', N '-tetraethyl-ethylene diamine, and N, N, N ', N ', N " five C
1-C
12Alkyl-C
1-C
3Two alkylene triamine, as N, N, N ', N ', N " five methyl diethylentriamine.
The non-proton chelating of inertia many (organic phosphine alkane) is P preferably, P, P ', P '-four C
1-C
12Alkyl-C
1-C
3Alkylidene group diphosphine alkane, as P, P, P ', P '-tetramethyl-ethylidene diphosphine alkane.
Particularly, glycol ether, many (organic amines) or many (organic phosphine alkane) comprise methyl, ethyl, propyl group or butyl group.
The assorted substitutive derivative of glycol ether, many (organic amines) and many (organic phosphine alkane) is also included within the scope of the present invention, as N, N-dimethyl-2-methoxy ethyl amine, N, N-dimethyl-2-ethoxyethyl group amine, N, N-dimethyl-3-METHOXY PROPYL AMINE, N, N-dimethyl-3-ethoxycarbonyl propyl amine, N, N-dimethyl-3-(2-methoxy ethoxy) propyl group amine [2.2.2]-kryptic acid.
The silane of Grignard reagent and general formula 3 is by 0.5: 1.0-1.0: 0.5, preferred 1.0: 0.8-1.0: 1.0 mol ratio is reacted.
In Grignard reagent, the addition of transition-metal catalyst is preferably 0.01-10mol%, is preferably 0.1-2mol% especially.
In Grignard reagent, the addition of chelate compound is the 1-20 equivalent, is preferably the 1-8 equivalent.Excessive greatly chelate compound can play the effect of thinner, to guarantee that reaction mixture is easy to stir when being settled out magnesium halide.Therefore, as the solvent of nonpolar alkane or aromatic compound not necessarily, but can not produce difficulty yet.
Reaction is preferably carried out under-30 to 160 ℃, preferred especially 0 to 120 ℃ temperature.
The silane of general formula 1 can randomly be distilled out as pure substance from reaction mixture by distillation, perhaps is distilled as corresponding solution after adding suitable solvent.
The silane of general formula 1 can be used in particular for organic compound is carried out silylanizing, for example comes synthetic drugs and analyzes usefulness.
In embodiment described below, except as otherwise noted, all part and percentage ratios all are meant weight part and weight percentage.Except as otherwise noted, under normal atmosphere and room temperature, carry out following examples, that is to say about 1000hPa and 20 ℃, perhaps temperature determined temperature when making reagent reach room temperature together when not extra heating or the cooling.Embodiment 1
At first under inert atmosphere the iodine of 48.6g (2.0mol) magnesium chips and a spatula point is introduced in 2 liters of three-necked flasks, this flask has accurate glassed agitator, seals graduated thermometer, Dimroth condenser and dropping funnel fully.Add 600ml ethylene glycol dimethyl ether and 203.7g (2.2mol) tertiary butyl chloride, make corresponding Grignard reagent thus--tertiary butyl chlorination magnesium.The cupric acetylacetonate (II) of Dropwise 5 .2g (0.02mol) at first is then at the dimethyl silicon dichloride that drips 232.3g (1.8mol) under 50 ℃ the temperature in 2 hours time.Temperature in the flask rises slightly, continues to stir the mixture 3 hours under 70 ℃ subsequently, so that reaction is carried out fully.For from solution, removing the magnesium salts that is settled out, in the atmosphere of inert gas argon, filter filter reaction mixture by pressurization and air extracting.The drip washing of filter cake spent glycol dimethyl ether.Last under normal pressure the filtrate of fractional distillation through merging, produce the t butyldimethylsilyl chloride (77% productive rate is in the dimethyl silicon dichloride) of 208.9g, it is white crystalline solid, purity be 95% (according to
1H-NMR).Embodiment 2
Repeat the step of embodiment 1, but do not use ethylene glycol dimethyl ether, and be to use other the non-proton chelating glycol ether of inertia.These researchs the results are shown in Table 1.
Table 1
1: isolated yield, content more than or equal to 95% (according to
1H-NMR) embodiment 3
| Glycol ether | Usage quantity (ml) | T butyldimethylsilyl chloride productive rate (%) 1 |
| Diethylene glycol dimethyl ether | ????800 | ????71 |
| The Diethylene Glycol dibutyl ether | ????800 | ????67 |
| The triethylene glycol dimethyl ether | ????800 | ????70 |
Repeat the step of embodiment 1, but do not use cupric acetylacetonate (II), and be to use other transition-metal catalyst.These researchs the results are shown in Table 2.
Table 2
1: isolated yield, content more than or equal to 95% (according to
1H-NMR) embodiment 4
| Transition-metal catalyst | Usage quantity (ml) | T butyldimethylsilyl chloride productive rate (%) 1 |
| Cupric chloride (I) | ????1 | ????64 |
| Cupric chloride (I) | ????5 | ????65 |
| Cupric bromide (I) | ????1 | ????70 |
| Cupric iodide (I) | ????1 | ????62 |
| Cupric oxide (I) | ????1 | ????27 |
| Cupric acetylacetonate (II) | ????5 | ????77 |
| Cupric chloride (II) | ????1 | ????69 |
| Methyl alcohol ketone (II) | ????1 | ????68 |
| Venus crystals (II) | ????1 | ????64 |
Repeat the step of embodiment 1, but in filtrate, add 280.0g toluene in distillation is subsequently handled, to obtain toluene solution rather than pure substance.Distill out the t butyldimethylsilyl chloride toluene solution of 440.0g, wherein the content of t butyldimethylsilyl chloride is 50 weight %.In the dimethyl silicon dichloride, this productive rate that is equivalent to t butyldimethylsilyl chloride is 81%.Embodiment 5
At first under inert atmosphere the iodine of 48.6g (2.0mol) magnesium chips and a spatula point is introduced in 2 liters of three-necked flasks, this flask has accurate glassed agitator, seals graduated thermometer, Dimroth condenser and dropping funnel fully.Add 600ml ethylene glycol dimethyl ether and 203.7g (2.2mol) tertiary butyl chloride, make tertiary butyl chlorination magnesium thus.The cupric acetylacetonate (II) of Dropwise 5 .2g (0.02mol) at first is then at the phenylbenzene silicon dichloride that drips 455.8g (1.8mol) under 50 ℃ the temperature in 2 hours time.Temperature in the flask rises slightly, continues to stir the mixture 3 hours under 70 ℃ subsequently, so that reaction is carried out fully.For from solution, removing the magnesium salts that is settled out, in the atmosphere of inert gas argon, filter filter reaction mixture by pressurization and air extracting.The drip washing of filter cake spent glycol dimethyl ether.Fractional distillation produces the tert-butyl diphenyl silicon chlorides (85% productive rate is in the phenylbenzene silicon dichloride) of 420.6g through the filtrate of merging under vacuum at last, and it is a colourless liquid, and the purity that records among the GC is 92%.
Claims (5)
1, the method for preparing the silane of general formula 1:
R
mR
1 nSiX
4-m-n(1) it is the Grignard reagent that makes general formula 2 when transition-metal catalyst and the non-proton chelate compound of inertia exist
R
1MgX
1(2) with the silane reaction of general formula 3,
R
mSiX
4-m(3) wherein:
The optional C that is replaced by fluorine, chlorine or cyano group of R representative
1-C
10Alkyl,
R
1On alpha-position with respect to Siliciumatom, the optional C that is replaced by fluorine, chlorine or cyano group of its representative
4-C
30The tertiary hydrocarbon base,
X and X
1Represent chlorine, bromine or iodine respectively,
M represents 2 or 3 numerical value, and
N represents 1 or 2 numerical value.
2, the method for claim 1, wherein R
1Be formula-CR
2 3The tertiary hydrocarbon base, R wherein
2Represent C
1-C
6-alkyl or C
1-C
6-alkylidene group phenyl.
3, as claim 1 and 2 described methods, wherein, radicals R is C
1-C
6-alkyl or phenyl.
4, as the described method of claim 1-3, wherein, using oxidation level be that+1 copper compound, oxidation level are that+2 copper compound or zn cpds are as transition-metal catalyst.
5, as the described method of claim 1-4, wherein, the non-proton chelate compound of described inertia is selected from: glycol ether, many (organic amines) or many (organic phosphine alkane) and their assorted substitutive derivative.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19837906A DE19837906C1 (en) | 1998-08-20 | 1998-08-20 | Preparation of organosilane derivatives |
| DE19837906.4 | 1998-08-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1245807A true CN1245807A (en) | 2000-03-01 |
Family
ID=7878218
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99111538A Pending CN1245807A (en) | 1998-08-20 | 1999-08-20 | Preparation method of silicane whose alpha-position related to silicon atom possesses tertiary alkyl radical |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US6156918A (en) |
| EP (1) | EP0980870B1 (en) |
| JP (1) | JP2000086675A (en) |
| CN (1) | CN1245807A (en) |
| AT (1) | ATE210668T1 (en) |
| CA (1) | CA2279739A1 (en) |
| DE (2) | DE19837906C1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102964371A (en) * | 2012-12-17 | 2013-03-13 | 上海化工研究院 | Preparation method of silicon-bridged sterically-hindered cyclopentadiene compound |
| CN109879902A (en) * | 2019-03-18 | 2019-06-14 | 山东东岳有机硅材料股份有限公司 | The synthetic method of cyano-containing organo-silicon compound |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6429327B1 (en) * | 1999-01-21 | 2002-08-06 | Fmc Corporation | Organometallic catalysts |
| JP3869177B2 (en) * | 2000-02-14 | 2007-01-17 | セントラル硝子株式会社 | Method for producing octafluoro [2,2] paracyclophane |
| JP6665437B2 (en) * | 2015-01-22 | 2020-03-13 | 東ソー株式会社 | Method for producing tertiary alkyl silane and tertiary alkyl alkoxy silane |
| CN113195506B (en) * | 2018-12-10 | 2024-07-30 | 恩特格里斯公司 | Preparation of triiodosilane |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3566888D1 (en) * | 1984-10-04 | 1989-01-26 | Ciba Geigy Ag | Silanes, process for their preparation and their use |
| JPH0786115B2 (en) * | 1989-06-28 | 1995-09-20 | 東レ・ダウコーニング・シリコーン株式会社 | Method for producing halogenated silane containing tertiary hydrocarbon group |
| JP2551901B2 (en) * | 1991-07-26 | 1996-11-06 | エフ エム シー コーポレーション | Contact alkylation method |
| JP2838342B2 (en) * | 1991-11-13 | 1998-12-16 | 信越化学工業株式会社 | Method for producing tertiary hydrocarbon silyl compound |
| JPH07157491A (en) * | 1993-12-03 | 1995-06-20 | Shin Etsu Chem Co Ltd | Production of silane containing tertiary hydrocarbon group at alpha-position |
| JP2854832B2 (en) * | 1995-03-10 | 1999-02-10 | 日東化成株式会社 | Method for producing silicon compound having steric hindrance |
| JP2867118B2 (en) * | 1995-03-16 | 1999-03-08 | 日東化成株式会社 | Method for producing silicon compound |
| JP3656168B2 (en) * | 1995-06-12 | 2005-06-08 | 日東化成株式会社 | Method for producing silicon compound bonded with halogen atom |
| US5872274A (en) * | 1998-06-11 | 1999-02-16 | Dow Corning Corporation | Method for preparation of tertiary-hydrocarbylsilyl compounds |
-
1998
- 1998-08-20 DE DE19837906A patent/DE19837906C1/en not_active Expired - Fee Related
-
1999
- 1999-07-01 AT AT99112748T patent/ATE210668T1/en not_active IP Right Cessation
- 1999-07-01 EP EP99112748A patent/EP0980870B1/en not_active Expired - Lifetime
- 1999-07-01 DE DE59900529T patent/DE59900529D1/en not_active Expired - Fee Related
- 1999-07-29 US US09/363,684 patent/US6156918A/en not_active Expired - Fee Related
- 1999-08-05 CA CA002279739A patent/CA2279739A1/en not_active Abandoned
- 1999-08-16 JP JP11229936A patent/JP2000086675A/en active Pending
- 1999-08-20 CN CN99111538A patent/CN1245807A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102964371A (en) * | 2012-12-17 | 2013-03-13 | 上海化工研究院 | Preparation method of silicon-bridged sterically-hindered cyclopentadiene compound |
| CN102964371B (en) * | 2012-12-17 | 2015-08-12 | 上海化工研究院 | A kind of preparation method of silicon bridge vicinal resistance type cyclopentadiene compounds |
| CN109879902A (en) * | 2019-03-18 | 2019-06-14 | 山东东岳有机硅材料股份有限公司 | The synthetic method of cyano-containing organo-silicon compound |
| CN109879902B (en) * | 2019-03-18 | 2021-07-09 | 山东东岳有机硅材料股份有限公司 | Method for synthesizing organosilicon compound containing cyano |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0980870A1 (en) | 2000-02-23 |
| US6156918A (en) | 2000-12-05 |
| DE59900529D1 (en) | 2002-01-24 |
| DE19837906C1 (en) | 1999-12-16 |
| JP2000086675A (en) | 2000-03-28 |
| ATE210668T1 (en) | 2001-12-15 |
| CA2279739A1 (en) | 2000-02-20 |
| EP0980870B1 (en) | 2001-12-12 |
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